SO₄^2-/SnO₂ Solid Superacid Granular Stacked One-Dimensional Hollow Nanofiber for a Highly Conductive Proton-Exchange...

A novel sulfated tin oxide solid superacid granular stacked one-dimensional (1D) hollow nanofiber (SO₄^2-/FSnO₂) is proposed as a nanofiller in sulfonated poly(phthalazinone ether sulfone ketone) (SPPESK) to manipulate a highly conductive proton nanochannel. It has unique microstructures with an open-end hollow nanofibric morphology and grain-stacked single-layer mesoporous fiber wall, which greatly enlarge the specific surface area and aspect ratio. The diverse acid sites, that is, SO₄^2-, Sn-OH Brönsted, and Sn⁴⁺ Lewis superacids, provide a high concentration of strong acidic proton carriers on the nanofiber surface and dynamically abundant hydrogen bonds for rapid proton transfer and interfacial interactions with -SO₃H groups in the SPPESK along the 1D hollow nanofiber. As a result, long-range orientated ionic clusters are observed in the SO₄^2-/FSnO₂ incorporated membrane, leading to simultaneous enhancement of proton conductivity (226.7 mS/cm at 80 °C), mechanical stability (31.4 MPa for the hydrated membrane), fuel permeation resistance, and single-cell performance (936.5 and 147.3 mW/cm² for H₂/O₂ and direct methanol fuel cells, respectively). The superior performance, as compared with that of the zero-dimensional nanoparticle-incorporated membrane, Nafion 115, and previously reported SPPESK-based membranes, suggests a great potential of elaborating superstructural 1D hollow nanofillers for highly conductive proton-exchange membranes.